FUNCTIONALIZED CURRENT COLLECTOR FOR ELECTROCHEMICAL DEVICES, WITH INCREASED RESISTANCE TO CORROSION

Abstract

 Current collector for electrochemical devices comprising a metal support in contact with an electrolyte containing a bistriflimide anion, hereafter named as TFSI^-, characterized in that said metal support comprises an electro-active surface which is functionalized with linear or branched fluorinated carbon chains, such as a perfluoroalkyl chains, in the form of a molecular layer which improves the corrosion resistance of said functionalized surface compared to a non-functionalized surface.
The invention also relates to the use of said current collector in a storage energy device, such as a lithium-ion, sodium-ion, aluminum-ion, calcium-ion or magnesium-ion battery, in a supercapacitor, in a photo-battery, or in an electro-chromic device, and to the process of functionalizing the active surface of the current collector.

Description

FIELD OF THE INVENTION

[0001] The present invention relates to the field of energy storage devices, lithium-ion, sodium-ion, magnesium-ion, calcium-ion or aluminum ion batteries, electrochemical capacitors so called supercapacitors, lithium-ion or sodium-ion capacitors, hybrid devices which are intermediate between batteries and supercapacitors, photo- batteries, or electro-chromic devices.

[0002] It applies more particularly to the field of the current collectors which are included in such batteries or devices.

BACKGROUND OF THE INVENTION

[0003] In such devices or batteries the current collector generally comprises a sheet of metal, mostly based on Aluminum to provide electrical connection to the electrolyte.

[0004] In devices or batteries, especially rechargeable lithium batteries, where the solid or liquid electrolyte includes a highly conductive salt such as the trifluorosulfonimide anion (TFSI^-), corrosion is often observed after several cycling or at high potentials. This is mainly a localized corrosion named pitting corrosion, which induces small holes in the metal of the current collector, modifying its properties and impairing its efficiency, and consequently impairing the efficiency of the battery or device.

[0005] In order to attenuate, or at least limit, the pitting corrosion several approaches have been proposed yet.

[0006] A first approach is to modify the electrolyte composition in contact with the current collector. Numerous attempts have been made, among others:

• Increasing the concentration of LiTFSI in the electrolyte of lithium-ion batteries (Kazuaki Inoue et al., "Suppression of aluminum corrosion by using high concentration of LiTFSI" in Journal of Power Sources, vol. 231, pp. 234-238, 2013);
• Incorporating nanoparticles in the LiTFSI electrolyte, for instance silica fume nanoparticles (Yangxing Li et al. "Attenuation of aluminum current collector corrosion in LiTFSI electrolytes using fumed silica nanoparticles" in Electrochemical and Solid-State Letters, vol. 7, pp. A228-A230, 2004);
• Adding a small amount of LiPF₆ in an electrolyte containing mainly LiTFSI as lithium salt (Mouad Dahbi et al. "Comparative study of EC/DMC LiTFSI and LiPF6 electrolytes for electrochemical storage" in Journal of Power Sources, vol. 196, pp. 9743-9750,2011);
• Using ionic liquid instead of the classical organic carbonates solvents (Ethylene carbonate EC, diethylcarbonate DEC, dimethylcarbonate DMC) in the electrolyte (C. Peng et al. "Anodic behavior of Al current collector in 1-alkyl-3-methylimidazolium bis [(trifluoromethyl) sulfonyl] amide ionic liquid electrolytes" in Journal of Power Sources, no. 173, pp. 510-517, 2007).

[0007] The technical solutions brought by this first approach modify the environment of the current collector. Such modifications or incorporation of additives lead to increased costs of the electrolyte.

[0008] Another approach is to replace the aluminum current collector by a new material, for instance a flexible film made of pyrolytic polyimide graphite as disclosed by P. Han et al. "Anticorrosive flexible pyrolytic polyimide graphite film as a cathode current collector in lithium bis(trifluoromethane sulfonyl)" in Electrochemistry Communications, pp. 70-73, 2014. This material is more expensive than aluminum sheet and less easy to process. Its use severely limits the number of possible applications.

[0009] Still another approach is to coat the aluminum current collector surface with a protective layer as disclosed in WO 2005/089390 and in US 2012/0121974 which describe a lithium-ion electrochemical cell, where the cathode current collector comprising aluminum or aluminum alloy has a protective, electronically conductive coating on its surface, made of substantially pure carbon or graphite or mixed with a polymer for good mechanical properties of the coating and good adhesion of the coating to the surface of the metal foil, this last embodiment being preferred in the art. In this case (carbon + polymer), the thickness of the coating is from 0.1 µm to 10 µm. However, example 1 of US 2012/0121974 demonstrates that the protective, conductive carbon coating by itself is not sufficient to prevent corrosion of aluminum current collector, and consequently disclose in further examples the addition of LiBOB or LiPF₆ to the electrolyte solution to inhibit corrosion.

[0010] Therefore the main objective of the present invention is to provide a current collector with improved anti-corrosion properties, preferably without modifying the electrolyte in contact with such current collector.

[0011] Another objective of the invention is to provide a current collector for electrochemical cells with improved corrosion resistance, in particular to pitting corrosion, and therefore extending the life of the device.

[0012] Another objective of the invention is to provide a current collector which will be corrosion resistant and heat resistant, of low cost and easily processable.

BRIEF SUMMARY OF THE INVENTION

[0013] The above drawbacks of the prior art current collectors are overcome by the current collector of the present invention where the current collector for electrochemical devices (Li-ion batteries, energy storage devices) comprising a metal support in contact with an electrolyte containing a bistriflimide anion, hereafter named TFSI^- anion, is characterized in that said metal support comprises an electro-active surface which is functionalized with fluorinated carbon chains, such as perfluoroalkyl chains, in the form of a molecular layer which improves the corrosion resistance of said functionalized surface compared to a non-functionalized surface.

[0014] The bistriflimide anion which is systematically known as bis(trifluoromethane)sulfonimide anion and colloquially known as TFSI^-, is a non-coordinating anion with the chemical formula [(CF₃SO₂)₂N]^- and developed formula :

[0015] In a preferred embodiment, the fluorinated carbon chains comprise perfluoroalkyl aryl moieties.

[0016] In particular, the perfluoroalkyl aryl moiety is preferably an aromatic cycle which is mono- or di- substituted by respectively one or two linear or branched perfluoroalkyl chain(s), preferably linear or branched perfluoro C₁ to C₂₀ alkyl chain(s), more preferably linear or branched perfluoro C₁ to C₁₀ alkyl chain(s).

[0017] For instance, the linear or branched fluorinated carbon chain may be a perfluoroalkyl chain chosen among the following groups: trifluoromethyl, perfluorohexyl and perfluorooctyl group.

[0018] The current collector may be an aluminum alloy or an aluminum substrate having a purity above 95 %, preferably a purity equal or above 99 %, or an aluminum alloy comprising more than 95 % Al, preferably more than 99 % Al.

[0019] In a first embodiment of the invention, the TFSI^- containing electrolyte is a liquid electrolyte, preferably an organic or ionic liquid electrolyte.

[0020] For instance, the TFSI^- electrolyte may be a mixture of a salt containing said TFSI^- anion (such as LiTFSI, NaTFSI and/or NH₄TFSI), and an organic solvent or mixture of organic solvents (such as propylene carbonate, dimethyl carbonate, ethyl carbonate, χ-butyrolactone), optionally containing additives (such as vinylene carbonate).

[0021] The TFSI^- electrolyte may also be a mixture of a salt containing said TFSI^- anion (such as LiTFSI, NaTFSI and/or NH4TFSI) dissolved in pure or diluted molten salts, systematically know as ionic liquids (such salts may be chosen among 1-Ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)-imide, N-Propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-Butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide).

[0022] The above list is not limitative and other solvents or ionic liquids that can dissolved TFSI^- based salts may be employed.

[0023] In a second embodiment of the invention, the TFSI- containing electrolyte is a solid electrolyte, preferably a polymer based electrolyte, or a physical ionogel, or a chemical ionogel.

[0024] As exemple of said solid electrolyte is preferably a mixture of a TFSI^- anion containing salt, such as LiTFSI, NaTFSI, or NH₄TFSI, and a polymer or mixture of polymer, such as poly(ethylene) oxide, and/or polyvinylidene fluoride.

[0025] As exemple of ionogel is preferably a mixture of a TFSI^- containing ionic liquid or an ionic liquid and a TFSI^- containing salt, such as LiTFSI, NaTFSI, or NH4TFSI, and a silica matrix or a mixture of silica and a polymer matrix.

[0026] Of course the above list is not limitative and any polymer exhibiting solvating properties or any ionogel in which TFSI^- based salt can be added may be employed.

[0027] As will be seen in the examples below, the molecular functionalized current collector of the present invention provides improved anti-corrosion properties, without requiring the use of an anti-corrosion additive in the electrolyte. This leads to improved life of the devices using said current collector.

[0028] Moreover this kind of current collector is a low cost current collector, which is easily processable, non toxic and heat resistant (up to 400°C).

[0029] The present invention also relates to the use of the above described current collector in an electrochemical device or a photo-electrochemical device, such as an energy storage device, a lithium-ion, a sodium-ion, a magnesium-ion, a calcium-ion or an aluminum ion battery (including metal-air batteries using one of the corresponding metal), an electrochemical capacitor so called supercapacitor, a lithium-ion or a sodium-ion capacitor, an hybrid device which is intermediate between battery and supercapacitor, a photo-battery, or an electro-chromic device.

[0030] In addition the present invention also relates to a process for preparing the above functionalized current collector, comprising the following main steps:

• Providing a current collector for electrochemical devices, said current collector comprising a support with a metallic surface;
• Polishing said metallic surface with a fine abrasive to remove any oxide layer, then washing said surface with an organic solvent under ultra-sonication to obtain a polished electro-active surface;
• Functionalizing the polished electro-active surface by dipping said surface of the current collector in a solution comprising a diazonium salt of a perfluoroalkyl moiety, preferably a perfluoroalkyl aryl moiety, under reducing conditions of the diazonium salt, and obtaining an electro-active surface functionalized with the perfluoroalkyl aryl moiety,
• Optionally washing the functionalized surface with an organic solvent under ultra-sonication, to remove the non-functionalized molecules from the electro-active surface of the support.

[0031] Preferably in the process according to the invention, the functionalized step is performed in an electrochemical cell, a photochemical cell, a heated cell or a sonicated cell and/or with the help of a chemical reducer in said solution.

[0032] The polishing step is preferably a dry polishing step. For instance, as will be shown in comparative example 3 below, better results are obtained with a dry polishing step when the metal support comprises aluminum.

[0033] The functionalizing step may be performed in a chronoamperometric cell containing a solution comprising a diazonium salt of the functionalizing perfluoroalkyl aryl moiety, an auxiliary electrode, a reference electrode and said metallic support as working electrode, at a potential under the redox potential of said diazonium salt of the functionalizing perfluoroalkyl aryl moiety.

[0034] Preferably, the auxiliary electrode is an electronically conductive plate, such as platinum, the reference electrode is Ag/AgCl and the working electrode is said metallic support made of an aluminum substrate having a purity above 95 %, preferably a purity equal or above 99 %, or made of an aluminum alloy comprising more than 95 % Al, preferably more than 99 % Al.

[0035] The preferred potential for the chronoamperometric functionalizing step is then of -0.9 V vs. Ag/AgCl.

[0036] These and other embodiments of the present invention will be more apparent when read with the following description of the examples in relationship with the attached following drawings:

BRIEF DESCRIPTION OF THE DRAWINGS

[0037] 

FIG.1 presents Nyquist diagrams, before cycling, of a unfunctionalized (non-treated) aluminum current collector and of a functionalized (treated) aluminum current collector according to the present invention;

FIG.2 is a schematic diagram equivalent electric circuit for interfaces of a unfunctionalized current collector;

FIG.3 is a schematic diagram equivalent electric circuit for interfaces of the functionalized current collector;

FIG.4 are linear sweep voltammetry curves of the functionalized and unfunctionalized aluminum substrates;

FIG.5A and FIG. 5B are scanning electron microscopy (SEM) pictures of respectively unfunctionalized (non-treated) aluminum substrate, and functionalized (treated) aluminum substrate according to the invention;

FIG.6 shows curves of galvanostatic cycling at cycle 1 (C/10) of functionalized and unfunctionalized current collectors;

FIG.7 shows curves of galvanostatic cycling at cycle 10 (C/10) of functionalized and unfunctionalized current collectors;

FIG.8 are linear sweep voltammetry curves of unfunctionalized and functionalized aluminum substrates of the comparative example 2.

DETAILED DESCRIPTION OF THE INVENTION

EXAMPLE 1

I/ Functionalization procedure of a current collector

I-a) Chemicals

[0038] All standard chemicals were purchased from Sigma Aldrich. In the examples the aniline precursor for preparing the diazonium salt was 4-(heptadecafluorooctyl) aniline, the reducing agent tert-butylnitrite and the electrolyte was tetraethylammonium tetrafluoroborate dissolved in acetonitrile. All those reactants were used as received.

I-b) Preparation of Aluminum substrates

[0039] A sheet (foil of 125 µm thickness) of non-allied aluminum was chosen with a purity of 99%. Before doing any functionalizing on this current collector the surface was dry polished using a finer abrasive (preferably grade 500) to remove the aluminum oxide layer, and then washed in a bath with acetone and ethanol using ultra-sonication.

I-c) Functionalization

[0040] Typical functionalizing experiments were carried out in open air at room temperature (20-25°C) and atmospheric pressure.

[0041] A first electrolyte solution of 0.1M tetraethylammonium tetrafluoroborate in acetonitrile was prepared. Then a second solution of diazonium salts (10mM) was prepared by adding 4-(heptadecafluorooctyl) aniline and 3 equivalents of tert-butylnitrite to the first solution. This "diazonium solution" was kept under stirring for 30 minutes arround.

[0042] Electrochemical functionalizing experiments were carried out in a three-electrode cell containing the "diazonium solution" and comprising a working electrode at which the functionalizing reaction takes place (aluminum sheet), an auxiliary electrode (platinum plate) and a reference electrode (Ag/AgCl). Chronoamperometry (CA) permitted to reduce the diazonium cations on the aluminum substrate to form a functionalized surface. The working electrode was polarized at -0.9V vs. Ag/AgCl for different periods of time (preferably at least 1 minute) according to the desired degree of functionalizing. At the end of the functionalizing process, the modified current collector was washed by dipping in acetone under ultrasonication to remove the unfunctionalized molecules from the aluminum surface.

II/ Characterisation of the functionalized surface

II-a) Surface modification

[0043] In order to measure the surface tension and also to observe the shape of a water drop on the substrate, the contact angles of each sample were measured 5 times using the sessile-drop method by dispensing 1 mL droplets on the sample surfaces. All of the contact angle measurements were taken under ambient laboratory conditions with a temperature of ~20°C and a relative humidity of ~45%.

[0044] In addition, the surface was watched with a scanning electron microscope and analyzed by X-ray dispersive spectroscopy. Results are presented in Table 1 below:

Table 1

Substrate	Functionalizing by CA	Water Contact Angle	Surface energy (mN m-1)			X-ray micro analysis (% mass fluorine)
			Total	Polar component	Dispersive component
Aluminum 99% - foil 125 µm	no	63	43	12	31	0.05 ± 0.06
	yes	92	20	5	15	0.30 ± 0.06

CA = chrono amperometry % mass fluorine given for a 100 x 100 x 1 µm3

[0045] A drastic increase of the % mass fluorine is observed and is assigned to the presence of perfluoroalkyl groups on the functionalized surface.

[0046] The contact angle of the water drop is higher for modified aluminum and the value of the polar component of surface energy decreases when the substrate is functionalized. All these results enable to conclude on the modification of aluminum surface samples by functionalizing a hydrophobic molecular layer.

II-b) Impedance spectroscopy

[0047] The impedance spectroscopy (see Nyquist's diagram on Figure 1) permits mainly to determine that the current collector surface has been modified by the functionalizing procedure. After establishment of a model (see Figures 2 and 3 and respective calculated values presented in tables 2 and 3) it is possible to notice a new input due to the functionalized layer.

Table 2

Index i	Ri (Ω)	Qi (F.s-1/ai)	ai
0	6	-	-
1	-	-	-
2	309	33 10-6	0.73
3	459	0.7 10-3	0.66

Table 3

Index i	Ri (Ω)	Qi (F.s-1/ai)	ai
0	6	-	-
1	14	2 10-6	0.1
2	423	29 10-6	0.75
3	264	0.9 10-3	0.68

[0048] This new input has a low resistance (14 Ω) and a constant phase element (CPE) of 2.10^-6 F s-^1/a. The calculated values indicates that this new input (due to the functionalized molecular layer) is weak and has little influence on the electron transfer. Therefore, it would not alter the basic requirements for a current collector.

III/ Effect of functionalizing

III-a) Linear Sweep Voltammetry

Electrochemical cell (SwageLock cell):

[0049] 

• Reference and counter electrode = lithium metal;
• Working electrode = aluminum (functionalized or non-functionalized surface);
• Electrolyte = LiTFSI 0.75M in EC:DEC (3:7).
  (EC = Ethylene carbonate / DEC = Diethylcarbonate)

Parameters:

[0050] 

• Speed rate = 1 mV s-1;
• Electrode surface = 1.13 cm²;
• E_min = Eoc (open-circuit voltage);
• E_max = 5 V vs. Li/Li⁺.

[0051] In this voltammetric method the current at a working electrode is measured while the potential between the working electrode and a reference electrode is swept linearly with time, from E_min to E_max at a determined speed rate. The selected area analyzed by this method is 1.2 cm² for all the samples. There are two phenomena to observe on Figure 4.

[0052] First of all the maximum current measured at 5V vs. Li/Li⁺ is totally different when the aluminum is functionalized or not. An impressive decrease of the maximum current of 80 % is observed when the aluminum current collector is functionalized by the functionalized molecules. Since the current is proportional to the corrosion rate this clearly indicates that the functionalizing treatment according to the present invention reduces aluminum pitting by a factor of at least 3.

[0053] The second interesting parameter is the potential value at which the current begins to raise, which corresponds to the potential at which the corrosion phenomenon begins. It is shown on the graph that the curve corresponding to the functionalized current collector begins to raise after the non-coated one.

[0054] So the functionalized surface according to the present invention increases the corrosion potential of the current collector from 3.9 V vs. Li/Li⁺ up to 4.2V vs. Li/Li⁺. This means that the functionalized current collector can be used at a higher potential than the unfunctionalized one, thus enabling to reach higher cell voltage when this functionalized current collector will be integrated in a real device. For an energy storage device, this would imply working with higher energy density in the device using the functionalized current collectors.

III-b) Scanning electron microscopy

[0055] SEM images were taken with secondary electron imaging mode and are presented in Figures 5A and 5B.

[0056] The corrosion of aluminum generally appears in the form of localized corrosions called pitting, i.e.: small holes created in the metal surface. Holes (5 to 20µm diameter) seen on the right picture (Figure 5A) are evidencing that the untreated current collector is quickly degraded by corrosion. The picture on the left (Figure 5B) shows the efficiency of the functionalized aluminum substrate according to the present invention with virtually no holes (no corrosion) thus confirming the electrochemical results presented above.

III-c) Galvanostatic cycling

Electrochemical cell:

[0057] 

• Reference and counter electrode = lithium metal;
• Working electrode = NMC (Nickel Manganese Cobalt) cathode (LiNi₁/3Mn₁/3Co₁/3O₂) casted on unfunctionalized or functionalized aluminum; this material is a standard material classically used as positive electrode in Li-ion batteries;
• Electrolyte = LiTFSI 0.75M in EC:DEC (3:7).
  (EC = Ethylene carbonate / DEC = Diethylcarbonate)

Parameters:

[0058] 

• Average mass of active material = 5 mg cm²;
• Average current = ± 136 µA;
• E_min = 2.7 V vs. Li/Li⁺;
• E_max = 4.2 V vs. Li/Li⁺;
• C/10.

[0059] The galvanostating cycling curves are presented on Figures 6 and 7 respectively corresponding to cycle 1 (C/10) and cycle 10 (C/10).

[0060] It can be noticed that the NMC electrode operates in the same manner whether the current collector surface is functionalized or not, which means that, as expected, the functionalizing treatment according to the present invention does not change the electrochemical behavior of the NMC cathode material.

[0061] The polarization is also an interesting phenomenon to look at. Indeed the potential width observed between the charge and the discharge is the same for all the batteries tested. The NMC cathode operates as usual when deposed on a treated current collector. Thus the functionalizing treatment prevents corrosion of the aluminum current collector without inhibiting the electrochemical performance of the NMC electrode.

EXAMPLE 2 (COMPARATIVE)

IV/ Functionalizing procedure of a non-fluorinated molecule

IV-a) Preparation of Aluminum substrates

[0062] A sheet (foil of 125 µm thickness) of non allied aluminum was chosen with a purity of 99%. Before doing any functionalizing on this current collector the surface was dry polished using a finer abrasive (500 grade) and then washed with acetone and ethanol under ultrasonication.

IV-b) Functionalizing

[0063] Typical functionalizing experiments were carried out in open air at room temperature (20-25°C) and atmospheric pressure.

[0064] A first solution of an electrolyte of 0.1 M tetraethylammonium tetrafluoroborate in acetonitrile was prepared. Then a second solution of diazonium salts (10mM) was prepared by adding 4-dodecyl aniline and 3 equivalents of tert-butyl nitrite to the first solution. This "diazonium solution" was kept under stirring for 30 minutes.

[0065] Electrochemical functionalizing experiments were carried out in a three-electrode cell containing the "diazonium solution" comprising a working electrode at which the functionalizing reaction takes place (aluminum sheet), an auxiliary electrode (platinum plate) and a reference electrode (Ag/AgCl). Chronoamperometry (CA) permitted to reduce the diazonium cations on the aluminum substrate to form a functionalized surface. The working electrode was polarized at -1.2V vs. Ag/AgCl for different periods of time according to the desired degree of functionalizing. At the end of the functionalizing process, the modified current collector was dipped in acetone under ultrasonication.

IV-c) Characterisation of functionalized surface

[0066] In order to measure the surface tension and also to observe the shape of a water drop on the substrate, the contact angles of each sample were measured 5 times using the sessile-drop method by dispensing 1 mL droplets on the sample surfaces. All of the contact angle measurements were taken under ambient laboratory conditions with a temperature of ~20°C and a relative humidity of ~45%.

[0067] Results are presented in Table 4 below:

Table 4

Substrate	Functionalizing step by CA	Functionalizing time (min)		Surface energies (mN m-1)
			Water Contact angle	Total	Polar component	Dispersive component
Aluminum 99% - foil 125 µm	no	-	63	43	12	31
	yes	5	88	28	4	24
		1	93	34	1	32

CA = chronoamperometry

[0068] The contact angle of the water drop is higher for functionalized aluminum and the value of the polar component of surface energy decrease when the substrate is functionalized.

[0069] All these results permit to conclude on the modification of aluminum surface samples by functionalizing a hydrophobic molecule layer.

IV-d) Effect of coating

Electrochemical cell:

[0070] 

• Reference and counter electrode = lithium metal ;
• Working electrode = aluminum (functionalized or non-functionalized) ;
• Electrolyte = LiTFSI 0.75M in EC:DEC (3:7).

Parameters:

[0071] 

• Speed rate = 1mV s^-1 ;
• Electrode surface = 1.13 cm² ;
• E_min = E_oc (open-circuit voltage) ;
• E_max = 5 V vs. Li/Li⁺.

[0072] In this voltammetric method the current at a working electrode is measured while the potential between the working electrode and a reference electrode is swept linearly from E_min to E_max at a fixed speed rate. As shown in figure 8, the curves are really similar: there is no reduction of the corrosion current at 5V vs. Li/Li⁺ and no rise decrease in the corrosion potential. The non-fluorinated molecule functionalized on the aluminum surface does not prevent the corrosion of the current collector.

EXAMPLE 3 (COMPARATIVE)

[0073] The influence of the polishing step has been tested. The support is an Aluminum Goodfellow sheet with a purity of 99%.

• The surface of aluminum has been polished with an abrasive paper 800.

[0074] The functionalizing treatment has then been performed by chronoamperometry according to the conditions described in example 1 (step I-c).

[0075] Comparative tests have been made, before and after functionalization, with the aluminum sheet without polishing, after polishing under water lubrification or with dry polishing. The results are presented in table 5 below:

Table 5

Polishing step	Contact angle (°) of a water drop	Contact angle (°) of a water drop
	BEFORE FUNCTIONNALIZATION	AFTER FUNCTIONNALIZATION
Without polishing	31 ± 2	36 ± 2
Water polishing	33 ± 2	48 ± 2
Dry polishing	35 ± 2	100 ± 2

[0076] It appears that the polishing step is an important step in the to functionalization treatment of the present invention, in particular for aluminum substrates. In fact the aluminum support surface needs to be polished without lubricant, more specifically without water. The polishing step aims to remove all or part of oxide layer and obtain an electro-active surface. If water is used during this step the oxide layer seems to be reformed instantly. Therefore dry polishing is much preferred.

Claims

1. Current collector for electrochemical devices comprising a metal support in contact with an electrolyte containing a bistriflimide anion, hereafter named as TFSI^-, characterized in that said metal support comprises an electro-active surface which is functionalized with linear or branched fluorinated carbon chains, such as a perfluoroalkyl chains, in the form of a molecular layer which improves the corrosion resistance of said functionalized surface compared to a non-functionalized surface.

2. Current collector according to claim 1, characterized in that the fluorinated carbon chains comprise perfluoroalkyl aryl moieties.

3. Current collector according to claim 1 or 2, characterized in that the perfluoroalkyl aryl moiety is an aromatic cycle which is mono- or di- substituted by respectively one or two linear or branched perfluoroalkyl chain(s), preferably linear or branched perfluoro C₁ to C₂₀ alkyl chain(s), more preferably linear or branched perfluoro C₁ to C₁₀ alkyl chain(s).

4. Current collector according to any of the preceding claims, characterized in that the linear or branched fluorinated carbon chain is a perfluoroalkyl chain chosen among the following groups: trifluoromethyl, perfluorohexyl and perfluorooctyl group.

5. Current collector according to any of the preceding claims, characterized in that the current collector is an aluminum substrate having a purity above 95 %, preferably a purity equal or above 99 % or an aluminum alloy comprising more than 95 % Al, preferably more than 99 % Al.

6. Current collector according to any of the preceding claims, characterized in that the TFSI^- containing electrolyte is a liquid electrolyte, preferably a mixture of a salt containing the TFSI^- anion, such as LiTFSI, NaTFSI, or NH₄TFSI, and an organic solvent or mixture of organic solvents or the former salts dissolved in pure or diluted molten salt, known as ionic liquids.

7. Current collector according to any of claims 1 to 5, characterized in that the TFSI^- containing electrolyte is a solid electrolyte, preferably a polymer based electrolyte, preferably a mixture of a salt containing this anion, such as LiTFSI, NaTFSI,or NH₄TFSI, and a polymer or mixture of polymer or a physical ionogel or a chemical ionogel comprising a silica matrix or a mixture of silica and a polymer matrix.

8. Use of the current collector according to any of the preceding claims, in an electrochemical device or a photo-electrochemical device, such as an energy storage device, a lithium-ion, sodium-ion, magnesium-ion, a calcium-ion or an aluminum battery, an electrochemical capacitor so called supercapacitor, a lithium-ion or a sodium-ion capacitor, an hybrid device intermediate between battery and supercapacitor, a photo-battery, or an electro-chromic device.

9. Process for preparing the functionalized current collector of any of claims 1 to 7 comprising the following main steps:

- Providing a current collector for electrochemical devices, said current collector comprising a support with a metallic surface;

- Polishing said metallic surface with a fine abrasive to remove any oxide layer, then washing said surface with an organic solvent under ultra-sonication to obtain a polished electro-active surface;

- Functionalizing the polished electro-active surface by dipping said surface of the current collector in a solution comprising a diazonium salt of a perfluoroalkyl moiety, preferably a perfluoroalkyl aryl moiety, under reducing conditions of the diazonium salt, and obtaining an electro-active surface functionalized with the perfluoroalkyl aryl moiety,

- Optionally washing the functionalized surface with an organic solvent under ultra-sonication, to remove the non-functionalized molecules from the electro-active surface of the support.

10. Process according to claim 9 wherein the functionalized step is performed in an electrochemical cell, a photochemical cell, a heated cell or a sonicated cell and/or with the help of a chemical reducer in said solution.

11. Process according to claim 9 or 10 wherein the polishing step is a dry polishing step.

12. Process according to any of claims 9 to 11 wherein the functionalizing step is performed in a chronoamperometric cell containing a solution comprising a diazonium salt of the functionalizing perfluoroalkyl aryl moiety, an auxiliary electrode, a reference electrode and said metallic support as working electrode, at a potential under the redox potential of said diazonium salt of the functionalizing perfluoroalkyl aryl moiety.

13. Process according to claim 12 wherein the auxiliary electrode is an electronically conductive plate, the reference electrode is Ag/AgCl and the working electrode is said metallic support made of an aluminum substrate having a purity above 95 %, preferably a purity equal or above 99 %, or made of an aluminum alloy comprising more than 95 % Al, preferably more than 99 % Al.

Drawing